Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/16—Bleaching ; Apparatus therefor with per compounds
  • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
  • D21C5/02—Working-up waste paper
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
  • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/64—Paper recycling

Definitions

• the present invention deals with a method of improving the efficiency of ozone in bleaching pulp generated from waste paper.
• EP-A-514,901 a method to remove color from a recycled pulp made of waste papers to contact said pulp with oxygen or an oxygen containing gas which oxygen reacts with the color-causing compounds present in said pulp thereby bleaching said recycled pulp to make a recycled paper product.
• This oxygen bleaching step already well-known from the literature, might be followed by subsequent steps comprising (z) ozone, hydrogen peroxide (P), etc.
• the pH of the pulp Prior to this oxygen stage or after, the pH of the pulp might be adjusted either at low pH or at high pH, avoiding the 8-10 pH zone. Subsequent Z, P, H stages might be provided.
• the results indicate a slight bleaching action of oxygen alone, which action is enhanced by further stages, already known for their bleaching actions.
• the brightness obtained (which is not indicated whether it is prior to or after reversion) is rarely above 80, usually with long sequences.
• French Patent 2,056,606 (Norman Liebergott) describes that it is known that small amounts of peroxide stabilizes ozone. Although this may be true, this does not address the issue of efficiency of the peroxide stabilization in its own right vis-a-vis avoiding the requirement of the addition of protecting agents for hydrogen peroxide.
• the invention relates to a method of bleaching recycled paper containing pulp characterized by submitting said pulp to a test procedure to determine whether the pulp is more reactive to ozone in acidic or alkaline conditions, implementing the proper pH on the pulp according to the highest brightness obtained in said test procedure, contacting said pulp with ozone in an ozone stage (Z) treatment including a brightness stabilizing step during or at the end of the ozone stage (Z) consisting of contacting said pulp with hydrogen peroxide in an amount ranging from 0.1 to 0.3% of the weight amount of pulp, (which amount is small compared to the usual amount of H 2 O 2 in a usual P stage which ranges between 1% and 2% of the weight amount of pulp). No washing step of the pulp being provided between the ozone stage (Z) and the hydrogen peroxide contacting step, and no protectors added to prevent hydrogen peroxide decomposition.
• the invention comprises (Z/P), (Z+P) or (ZP) sequences, but not the ZP sequence (including a washing step between Z and P) as far as the amount of H 2 O 2 is outside the range defined hereabove.
• Z/P will be used herein to define the above sequences according to the invention.
• a preacidification stage before the Z/P sequence gives improved results regarding the brightness of the pulp.
• this preacidification step will be carried out with acids such as sulfuric acid, oxalic acid, or their mixtures to reach a pH preferably between 2 and 3, more preferably about 2.5. It is believed that this preacidification step allows to solubilize metal ions which might be present in the pulp. As this acidification step takes place in a medium consistency pulp, a subsequent dewatering and/or washing step helps to remove the solubilized metal ions which are supposed to create some decomposition of the hydrogen peroxide.
• the ozone stage could be carried out at a non adjusted pH which is the pH of the recycled pulp after the previous treatments.
• this Z stage treatment it is preferred to make this Z stage treatment at a pH which is either acidic, preferably lower than 4, and preferably comprised between about 2 and 3, while about 2.5 seems to be the preferred value or alkaline and preferably between about 9 to 11.
• the samples are then dewatered in preparation for next Z stages. Then high consistency samples are made from those three samples, which are contacted with ozone (1% by weight of the pulp) during e.g. 6 minutes.
• ozone 1% by weight of the pulp
• the highest BRIGHTNESS obtained indicates the proper pH to be implemented on the pulp during the ozone bleaching process according to the invention.
• any usual stage can be applied to the pulp either before the Z/P or AZ/P sequence (A means preacidification followed by dewatering and/or washing) or after said sequence.
• the brightness can be improved if either a Y stage or a FAS stage is applied.
• a Y stage is defined as a Sodium Hydrosulfite stage, while a FAS stage means applying Formamidine Sulfinic Acid stage.
• the invention is essentially based on the unexpected results obtained with an ozone bleaching stage wherein a small amount of hydrogen peroxide is added to the pulp during or at the end of the Z stage, preferably with a prior acidification step.
• the different steps of this stage are disclosed hereunder in greater details:
• Acid is added to the pulp to reach a pH between 2 and 3, preferably 2.5. At this point, low or medium consistency may be used. Acids as oxalic, sulfuric and others can be used for this purpose. The use of sulfuric acid is particularly efficient when the acidic step is carried out at temperatures between 50 and 90°C. Oxalic acid performs well at room temperature (20-25°C).
• the sample is dewatered to remove undesirable metal ions.
• a regular washing step will help to remove ions from the pulp.
• the degree of dewatering-washing will be dependent on the type of technology (high, medium or low consistency) that would be used in the next ozone stage. For example, if the ozone treatment is carried out at high consistency (35-45%), the excess of water present in the furnish during acidification has to be removed using regular equipment (twin press, etc.).
• High or medium consistency technology can be used to apply ozone to the pulp.
• High consistency requires the pulp to be fluffed.
• concentration of ozone in a carrier gas e.g. oxygen
• Pressure of the gas is about 1.5 atm.
• Temperature of the reaction ranges from 10 to 60°C. Higher temperatures may decompose ozone, making the reaction less efficient. Reaction time is short, and varies according to reactors configuration.
• the charge of ozone may vary according to the targeted brightness.
• the charge of ozone on dry pulp ranges between 0.3 and 1.5% by weight of pulp.
• this ozone stage according to the invention comprises also contacting the pulp with a small amount of hydrogen peroxide which ranges usually between 0.1% to 0.3% by weight of pulp.
• Ozone is usually contacted with the pulp as a mixture with oxygen or any other suitable carrier gas.
• the mixture comprises 0.1% to 14% by weight of O 3 in the carrier gas, and preferably between 0.1% to 10% by weight of ozone in the carrier gas, based on oxygen as the carrier gas (the proportion by weight being different with a carrier gas having a molecular weight different from that of oxygen).
• hydrogen peroxide should take place immediately after the pulp reacted with ozone.
• hydrogen peroxide may be introduced in a mixer at the discharge of the reactor, following the injection of alkali necessary to bring the pH of the pulp to about 11.0.
• peroxide can be injected in a fluidizing mixer after the pulp is separated from the reaction gases from the ozone stage. According to the invention, no washing nor dewatering are needed between the ozone reactor and the injection of alkali and hydrogen peroxide.
• a P stage can be carried out, preferably if acidification has been carried out before the Z/P stage. Since metal ions were already removed in certain extent by the acidification step, the P stage does not require protectors such as DTPA or silicates to prevent H 2 O 2 decomposition and to make the stage more efficient.
• Peroxide preferably 0.1-1.0% by weight of dry pulp
• the ozone is injected in the pulp either as a mixture of ozone and oxygen, usually directly from the ozonator or, as a mixture of ozone and another carrier gas, usually an inert gas such as nitrogen.
• an inert gas such as nitrogen.
• any other inert gas can be used such as argon, helium, xenon, krypton, neon and/or carbon dioxide or any mixtures thereof.
• Such mixtures are prepared by separating ozone from oxygen at the output of the ozonator, e.g. with a cryogenic trap and then desorbing the ozone with the other gas or gas mixture.
• the percentage by weight of ozone in the gas mixture can be varied (as far as the technique to produce ozone permits) within a large range, usually between 1% to 12% or more if the technique is available, preferably between the effective bleaching amount which is usually at least 0.1% by weight of dry pulp to about 7-8% or more if the technique is available.
• ozone on pulp means 1 gram ozone per 100 grams of dry pulp or 10 kg per metric ton of dry pulp, etc.
• the ozone generator produces ozone according to a well known method from the artisan from an oxygen flow.
• the gaseous stream from said ozone generator usually contains less than 10% by weight of ozone in oxygen and usually by 3% to 4% by weight.
• the mixture of oxygen and ozone is of course injected in the evaporator.
• the amount of ozone injected was determined by the injection duration and according to ozone concentration. Said ozone concentration is measured by iodometric titration of a KI solution contained in a gas washing bottle that collects the outlet gases of the system.
• the ozone rate of production is then determined as mg of ozone per minute.
• the ratio of the weight of ozone and the weight of dry pulp was 1.0%, the injection duration being about 6 minutes.
• Hydrogen peroxide (0.7%), 2% silicate and 0.2% DTPA were added to one preacidified sample (No. 1) and one non-preacidified sample (No. 3).
• Fluorescence of the sample is designated as Fl. L, a and b are different values measured which characterize certain colors of the sample, as usually used by the man skilled in the art and defined in fig. 3 of B. Van Lierop and N. Liebergott publication referred to hereabove.
• A means an acidification step at pH 2.5 followed by dewatering of the pulp.
• Zn is an ozone stage at not adjusted pH (pH of 8.5 in the present case).
• Za is an ozone stage at pH 2.5.
• Zb is an ozone stage at pH 10.
• the ozone consumption was 0.5% by weight of the weight of the pulp, except for sample (5) wherein 1% ozone was used.
• P- indicates 0.1% by weight of H 2 O 2 based on the weight of pulp, without additives.
• the retention time RT was 15 minutes and the temperature to carry out all of these stages was 50°C.
• the ozone was injected in the pulp with oxygen as a carrier gas, the gas mixture comprising 3.5% by weight of ozone and 96.5% by weight of oxygen.
• the duration of the contact between ozone and pulp was about 3 minutes to have 0.5% of ozone and was about 6 minutes to have 1% of ozone based on dry pulp weight.
• nitrogen gas or any inert gas can replace O 2 with similar results.
• samples 9 and 10 were treated with pure oxygen (no ozone), under exactly the same conditions as ozone in the other examples: the oxygen as a carrier gas was sent to the ozonator, but the ozonator was shut off, i.e. no ozone was produced.
• the treatment was applied to the sample, under alkaline or acidic conditions during the same exposure time, (about 3 minutes) and at room temperature, as the samples treated with ozone (1-8).
• Sample 5 is a "Zb" stage in which the consumption of ozone was set on 1.0% (twice the consumption of the other samples). Notice that although the brightness achieved is high (85.5%), the brightness after reversion is high as well (3.6 points).
• the peroxide addition can take place at the discharge of the ozone reactor and does not require stabilizers (DTPA, silicate, etc.) nor long retention time or high temperatures.
• A indicates an acidification stage
• AZ an acidification stage followed by an ozone stage in acidic conditions
• bZ means that the ozone stage is carried out at an alkaline pH (whether or not A was carried out before)
• Z/P- means that the ozone stage is followed according to the invention by an addition of a low amount of hydrogen peroxide without additives and with no washing or dewatering in between.
• comparison between 15 and 17 indicates that the sequences A Z or A b Z are similar: after an acidification stage A, a Z stage can be applied under acidic or alkaline conditions. However, comparison between 16 and 17 indicate that if the sample is not preacidified, then the Z treatment in alkaline conditions (b) is not as good as a Z treatment with a previous acidification stage A (followed by washing or dewatering as the upper case A indicates).

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Paper (AREA)

Applications Claiming Priority (3)

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• 1994
  • 1994-04-05 DK DK94913541T patent/DK0644965T3/da active
  • 1994-04-05 CA CA 2137450 patent/CA2137450C/en not_active Expired - Fee Related
  • 1994-04-05 EP EP19940913541 patent/EP0644965B1/en not_active Expired - Lifetime
  • 1994-04-05 WO PCT/EP1994/001068 patent/WO1994023117A2/en active IP Right Grant
  • 1994-04-05 DE DE1994608065 patent/DE69408065T2/de not_active Expired - Fee Related
  • 1994-04-05 BR BR9404892A patent/BR9404892A/pt not_active IP Right Cessation
  • 1994-04-05 ES ES94913541T patent/ES2111298T3/es not_active Expired - Lifetime
  • 1994-12-05 FI FI945721A patent/FI945721A/fi unknown
  • 1994-12-06 NO NO944696A patent/NO944696L/no not_active IP Right Cessation
• 1997
  • 1997-01-08 US US08/780,469 patent/US5755925A/en not_active Expired - Fee Related

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